高盐强酸性地下水中复合苯系污染物原位芬顿氧化实验研究

郭威; 袁放; 张佳; 谢斌; 冯学洋; 陈鸿汉

doi:10.16030/j.cnki.issn.1000-3665.202012021

高盐强酸性地下水中复合苯系污染物原位芬顿氧化实验研究

1.
中国地质大学（北京）水资源与环境学院北京市重点实验室，北京　100083

2.
中卫市生态环境监测站，宁夏中卫　755000

基金项目: 国家重点研发计划项目资助（2018YFC1800400）

详细信息

作者简介: 郭威（1996-），男，硕士研究生，研究方向为地下水环境。E-mail： guow163163@163.com

通讯作者: 陈鸿汉（1956-），男，博士，教授，博士生导师，主要从事地下水污染评价与防治技术研究。E-mail： chenhh@cugb.edu.cn

中图分类号: X523

收稿日期: 2020-12-11

修回日期: 2021-01-31

刊出日期: 2021-03-15

In-situ Fenton oxidation experiment of compound benzene pollutants in high salt and strong acid groundwater

1.
Beijing Key Laboratory of School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing　100083, China

2.
Ecological Environment Monitoring Station, Zhongwei, Ningxia　755000, China

More Information

Corresponding author: CHEN Honghan, chenhh@cugb.edu.cn

Received Date: 11 December 2020

Revised Date: 31 January 2021

Publish Date: 15 March 2021

摘要

摘要:
在原位氧化过程中，实际场地地下水和含水介质的物化特征是影响氧化效果的重要因素，而目前对此影响的研究较少。以某场地实际高盐强酸性复合苯系污染地下水为研究对象，以地下水中2-硝基-4-甲氧基苯胺（2-nitro-4-methoxyaniline，2-N）和3-硝基-4-甲氧基苯胺（3-nitro-4-methoxyaniline，3-N）为特征污染物，探究芬顿（Fenton）试剂原位氧化特征，并研究液相环境因素（初始H₂O₂浓度、初始Fe²⁺浓度、初始pH值、初始醋酸（Acetic acid，HAc）浓度、初始 ${\rm{SO}}_4^{2-}$ < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210203181048.png'/ > < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210203181048.png'/ > < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210203181048.png'/ > 浓度）以及含水层介质对Fenton法去除2-N和3-N的影响。结果显示：（1）Fenton法去除2-N和3-N效果显著，且在初始液相条件为c（H₂O₂）=7 mmol/L、c（Fe²⁺）=4 mmol/L、pH=4、c（HAc）=0 mg/L和c（ ${\rm{SO}}_4^{2-} $ < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210203181118.png'/ > < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210203181118.png'/ > < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210203181118.png'/ > ）=0 mmol/L时去除效果最佳；（2）各因素对Fenton法氧化2-N和3-N的影响不同，加入H₂O₂和Fe²⁺使2-N和3-N去除率上升，增大HAc浓度使2-N和3-N去除率下降；（3）含水层介质对2-N和3-N具有一定吸附性，且对3-N的吸附性强于2-N，二者在本实验中最大吸附态占比分别为29%和42%，而吸附态的存在会抑制Fenton法对2-N和3-N的去除；（4）矿物分析结果显示介质含有少量黄铁矿，在硫酸环境下，介质腐蚀溶解释放Fe²⁺，在达到一定浓度后，无需额外添加Fe²⁺即可完成Fenton反应进而去除2-N和3-N。
- 芬顿 /
- 原位氧化 /
- 2-硝基-4-甲氧基苯胺 /
- 3-硝基-4-甲氧基苯胺 /
- 地下水污染 /
- 含水层介质
Abstract:
In the process of in-situ oxidation, the physical and chemical characteristics of actual ground water and water-bearing media are the important factors affecting the oxidation effect, but there are few specific studies on this effect at present. The actual high-salt and strong-acid compound benzene contaminated groundwater in a certain site is used as the research object, and 2-nitro-4-methoxyaniline (2-N) and 3-nitro-4-methoxyaniline (3-N) in groundwater are characteristic pollutants. The in-situ oxidation characteristics of Fenton’s reagent are explored, and the liquid environmental factors (initial H₂O₂ concentration, initial Fe²⁺ concentration, initial pH value, initial acetic acid (HAc) concentration, initial ${\rm{SO}}_4^{2-} $ < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210310112508.png'/ > < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210310112515.png'/ > < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210310112515.png'/ > < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210310112515.png'/ > concentration) and aquifer media on the removal of 2-N and 3-N by Fenton method are examined. The results show that (1) the Fenton method has a significant effect on removal of 2-N and 3-N, and when the initial liquid phase conditions are c(H₂O₂)=7 mmol/L, c(Fe²⁺)=4 mmol/L, pH=4, c(HAc)=0 mg/L and c( ${\rm{SO}}_4^{2-} $ < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210310112508.png'/ > < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210310112515.png'/ > < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210310112515.png'/ > < img text_id='' class='formula-img' style='display:none;' src='202012021_Z-20210310112515.png'/ > )=0 mmol/L, the removal effect is the best. (2) Each factor affects the oxidation of 2-N and 3-N by the Fenton method. The effect of the addition of H₂O₂ and Fe²⁺ increases the removal rate of 2-N and 3-N. Increase in the concentration of HAc decreases the removal rate of 2-N and 3-N. (3) The groundwater medium has a strong effect on 2-N and 3-N, and the adsorption of 3-N is stronger than that of 2-N. In this experiment, the two largest adsorption states accounte for 29 % and 42 %, respectively. The existence of the adsorption state will inhibit the Fenton method to 2-N. (4) The mineral analysis results show that the medium contains a small amount of pyrite. In a sulfuric acid environment, the medium corrodes and dissolves to release Fe²⁺. Therefore, the Fenton reaction can be completed without additional Fe²⁺ to remove 2-N and 3-N.
- Fenton /
- in situ oxidation /
- 2-nitro-4-methoxyaniline /
- 3-nitro-4-methoxyaniline /
- groundwater pollution /
- aqueous medium

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图 1 地下水液相环境各要素对氧化影响

Figure 1.

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图 2 醋酸环境不同初始条件下介质对氧化影响

Figure 2.

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图 3 醋酸环境反应前后体系c（Fe²⁺）变化

Figure 3.

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图 4 醋酸环境反应前后体系pH值变化

Figure 4.

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图 5 不同介质电镜扫描图

Figure 5.

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图 6 硫酸环境下介质对氧化影响

Figure 6.

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图 7 硫酸处理后介质电镜扫描图

Figure 7.

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图 8 硫酸环境反应前后体系pH、c（Fe²⁺）变化

Figure 8.

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图 9 介质元素分布柱状图

Figure 9.

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表 1 场地地下水特征污染物浓度

Table 1. Concentrations of the characteristic pollutants in groundwater of the site

指标	2-N/（mg·L⁻¹）	3-N/（mg·L⁻¹）	HAc/（g·L⁻¹）	/（g·L⁻¹）	pH
浓度	32.78	60.58	1.06×10⁴	4.04×10³	4.18

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表 2 实验方案概括表

Table 2. Summary of the experimental program

序号	实验类型	序号	实验内容	影响因素初始值(X)
1	纯液相环境	1.1	初始H₂O₂浓度的影响	c（H₂O₂）=0，1，2，4，6，7 mmol/L
		1.2	初始Fe²⁺浓度的影响	c（Fe²⁺）=0，0.1，0.2，0.4，0.6，0.8，1.0，1.5，2.0，2.5，3.0，4.0 mmol/L
		1.3	初始pH值的影响	pH=2，3，4，5，6，7
		1.4	初始HAc浓度的影响	c（HAc）=1，10，20，30，40，50，60，70，80 g/L
		1.5	初始浓度的影响	c（）=0，2，4，6，8，10 g/L
2	固液双相环境	2.1	醋酸环境介质影响-不加Fe²⁺	介质质量：1，2，3，4，5 g
		2.1	醋酸环境介质影响-添加Fe²⁺	介质质量：1，2，3，4，5 g
		2.2	硫酸环境介质影响实验	介质质量：1，2，3，4，5 g

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表 3 各实验初始条件对照表

Table 3. Comparison of the initial conditions of each experiment

实验影响因素	2-N/（mg·L⁻¹）	3-N/（mg·L⁻¹）	H₂O₂/（mmol·L⁻¹）	Fe²⁺/（mmol·L⁻¹）	pH	HAc/（g·L⁻¹）	/（g·L⁻¹）	介质/g
初始H₂O₂浓度的影响	30	60	X	4	4	0	0	0
初始Fe²⁺浓度的影响	30	60	7	X	4	0	0	0
初始pH值的影响	30	60	7	4	X	0	0	0
初始HAc浓度的影响	30	60	7	4	4	X	0	0
初始浓度的影响	30	60	7	4	4	0	X	0
醋酸环境介质影响-不加Fe²⁺	30	60	7	0	4	60	0	X
醋酸环境介质影响-添加Fe²⁺	30	60	7	4	4	60	0	X
硫酸环境介质影响实验	30	60	7	0	4	0	9.6	X
注：表3中的X表示表2影响因素初始值一列中对应实验内容的数值。

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表 4 含水层介质中各矿物质量占比

Table 4. Mass ratio of each mineral in the aquifer medium

矿物名称	石英	斜长石	微斜长石	云母	方解石	绿泥石	白云石	黄铁矿
质量百分比/%	43	26	9	9	5	4	3	1

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